Inspired by the self-assembled bilayer structures of natural amphiphilic phospholipids, a new class of highly luminescent click-phospholes with exocyclic alkynyl group at the phosphorus center is reported. These molecules can be easily functionalized with a self-assembly group to generate neutral phosphole-lipids. This novel approach retains the versatile reactivity of the phosphorus center, allowing further engineering of the photophysical and self-assembly properties of the materials at a molecular level. The results of this study highlight the importance of being able to balance weak intermolecular interactions for controlling the self-assembly properties of soft materials. Only molecules with the appropriate set of intermolecular arrangement/interactions show both organogel and liquid crystal mesophases with well-ordered microstructures. Moreover, an efficient energy transfer of the luminescent materials is demonstrated and applied in the detection of organic solvent vapors.